Electron Affinities of the Early Lanthanide Monoxide Molecules

Abstract

The photoelectron imagings of LaO − , CeO − , PrO − , and NdO − at 1064 nm are reported. The well resolved photoelectron spectra allow the electron affinities to be determined as 0.99(1) eV for LaO, 1.00(1) eV for CeO, 1.00(1) eV for PrO, and 1.01(1) eV for NdO, respectively. Density functional calculations and natural atomic orbital analyses show that the 4f electrons tend to be localized and suffer little from the charge states of the molecules. The photodetached electron mainly originates from the 6s orbital of the metals. The ligand field theory with the δ=2 assumption is still an effective method to analyze the ground states of the neutral and anionic lanthanide monoxides.

Electronic structure of NdO via slow photoelectron velocity-map imaging spectroscopy of NdO¯

“…This, combined with the excellent agreement between the positions of features A-G with the term energies from fluorescence measurements, as well as the spacing of low-lying CASSCF states of NdO, confirms that peak A represents photodetachment to the ground state of neutral NdO. We thus report an electron affinity for NdO of 1.0091 (7) eV determined by the eBE of peak A, representing a significant improvement over the previously reported value of 1.01(1) eV, 23 and comparing favorably to our calculated value of 1.0034 eV at the SFX2C-1e-CCSD(T)/cc-pVTZ-X2C level.…”

“…18 A large number of electronic states of SmO were reported from slow photoelectron velocity-map imaging spectroscopy of cold SmO¯ (cryo-SEVI). 22 Previous photoelectron spectra of NdO¯ found the electron affinity (EA) of NdO to be 1.01(1) eV, 23 and emission and absorption lines of NdO have been reported in the region between 9500 -20000 cm -1 at modest resolution. 24,25 A large number of bands at higher resolution were measured lying between 7500 and 12600 cm -1 , 26 and laser induced fluorescence (LIF) identified low lying states in agreement with ligand field theory.…”

In situ formation and characterisation of singly ionised atomic europium in rare gas matrices—Luminescence spectroscopy and MP2 calculations

“…38 If present in appreciable quantities, the oxide could play a role as an electron scavenger. Once again because of the high vacuum maintained in this series of experiments, we do not consider any oxide (Eu-O x ) was produced from the in situ reaction of atomic europium with molecular oxygen.…”

The electronic configurations of LnX (Ln=La–Eu, X=O, S, Se, Te): A FON–DFT investigation

“…The LnO and LnS molecules have been studied at ligand field theory (LFT) [1][2][3][4][5], intermediate neglect of differential overlaps (INDO) [6], density functional theory (DFT) [7][8][9][10][11][12][13][14][15][16][17][18] and configuration interaction/coupled cluster with singles and doubles (CISD/CCSD) [19][20][21] levels with pseudopotential or frozen core approximations, while the theoretical literatures on LnSe and LnTe are few [15]. Wang and Schwarz in 1995 [8] studied the properties of LnO (Ln = La, Eu, Gd, Yb) and found a 4f 13 r 1 /4f 14 r 0 mixed ground state for YbO, which is stabler than either 4f 13 r 1 or 4f 14 r 0 .…”